CN1307596A - Method for producing supported catalyst system - Google Patents

Method for producing supported catalyst system Download PDF

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CN1307596A
CN1307596A CN99807826A CN99807826A CN1307596A CN 1307596 A CN1307596 A CN 1307596A CN 99807826 A CN99807826 A CN 99807826A CN 99807826 A CN99807826 A CN 99807826A CN 1307596 A CN1307596 A CN 1307596A
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alkyl
aryl
carbon atom
supported catalyst
lewis base
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M·O·克里斯滕
H·格里戈里乌斯
U·里夫
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Basell Polyolefine GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a method for producing a supported catalyst system, comprising the following steps: A) reacting an inorganic support material with an organometallic compound (I); B) reacting the support material obtained according to A) with a metallocene complex and a metallocenium ion-forming compound and C) subsequent reaction with an organometallic compound (II), the resulting supported catalyst or its precursor being brought into contact with 0.1 to less than 10 ml per mol of a Lewis base per mol of metallocene complex.

Description

The preparation of supported catalyst system
The present invention relates to a kind of method for preparing supported catalyst, comprise the following steps:
A) metallic compound of a kind of inorganic carrier material and general formula I is reacted:
M 1(R 1) r(R 2) s(R 3) t(R 4) uI here
M 1Be the III of basic metal, alkaline-earth metal or the periodic table of elements or the metal of IV main group,
R 1Be hydrogen, C 1-C 10Alkyl, C 6-C 15Aryl, each is at the alkylaryl or the arylalkyl that 1-10 carbon atom are arranged on the alkyl and 6-20 carbon atom arranged on aryl,
R 2-R 4Be hydrogen, halogen, C 1-C 10Alkyl, C 6-C 15Aryl, each is at the alkylaryl, arylalkyl, alkoxyl group or the dialkyl amido that 1-10 carbon atom are arranged on the alkyl and 6-20 carbon atom arranged on aryl,
R is the integer of 1-4
With
S, t and u are the integers of 0-3, and wherein, the summation of r+s+t+u is equivalent to M 1Valency,
B) make as A) described in the material that obtains with metallocene complex with can form metallocene ionic compound and react, and
C) material of gained and the metallic compound of general formula I I are reacted:
M 2(R 5) o(R 6) p(R 7) qII is wherein:
M 2Be the metal of the III main group of basic metal, alkaline-earth metal or the periodic table of elements,
R 5Be hydrogen, C 1-C 10Alkyl, C 6-C 15Aryl, each is at the alkylaryl or the arylalkyl that 1-10 carbon atom are arranged on the alkyl and 6-20 carbon atom arranged on aryl,
R 6And R 7Be hydrogen, halogen, C 1-C 10Alkyl, C 6-C 15Aryl, each is at the alkylaryl, arylalkyl or the alkoxyl group that 1-10 carbon atom are arranged on the alkyl and 6-20 carbon atom arranged on aryl,
O is the integer of 1-3,
With
P and q are the integers of 0-2, and here, the summation of o+p+q is equivalent to M 2Valency.
The invention still further relates to a kind of supported catalyst system that obtains by method of the present invention, and this catalyzer is at polymerization in homogeneous phase or ethene or the propylene and the C of ethene or propylene 3-C 10Application in the copolymerization of-alpha-olefin and the vapour phase polymerization of alkene.
Particularly for the vapour phase polymerization and the suspension polymerization of ethene or higher alpha-olefin, it is preferred using the supported catalyst system.Particularly can produce polymeric articles with elite clone performance by the metallocene catalyst on the carrier.
In order to utilize its whole catalytic activitys, many metallocene complexes need activation.As activating compounds, usually (for example utilize Lv oxane class, see EP-B1-035 242) or can be transformed into the metallocene oxonium ion to metallocene and stablize the compound (for example, seeing EP-A-277 004) of the unsaturated oxonium ion structure of this coordinate by suitable non-coordination gegenion.
The productivity of this catalyst system and therefrom economic operability obviously depend on the kind of carrier and particularly be coated to method on the carrier.A kind of particularly very effective method of the activable metallocene catalyst system of positively charged ion that applies on carrier has been described in DE-A 19 606 167.
For the productivity of the metallocene catalyst that improves cationic activation, in such catalyst system, add weak coordinate Lewis base (with reference to EP-B1-0648 786 and EP-A1-0 771 822).Yet these catalyst system great majority are homogeneous, non-supported catalyst system.With respect to metallocene complex, always use Lewis base with at least 10 times of molar excess, common excessive 50-250 is doubly.Though EP-A-0 771 822 has described metallocene complex and also can be applied on the carrier,, Lewis base always joins in the polyblend with soluble form and a large amount of excessive mode.
Owing to add the Lewis base of higher concentration metallocene catalyst there is restraining effect, in addition, the useless composition that extracts is arranged in polymkeric substance, so, wish to reduce the concentration of Lewis base, keep the advantageous effect of these compounds simultaneously catalyst productivity.
The objective of the invention is to seek a kind of method for preparing the metallocene catalyst system on the carrier, it no longer includes the shortcoming of prior art, and when adding a small amount of Lewis base, shows high productivity.
We have found that, the method of describing during by beginning for preparing supported catalyst has reached this purpose, it is characterized in that, obtain described supported catalyst in this way, its precursor is contacted with the Lewis base of every mole of metallocene complex 0.1-＜10 mole dosage.
In addition, obtain a kind of supported catalyst system by this method, with and the application of this supported catalyst system in the polymerization in homogeneous phase of alkene and copolymerization.
Supported catalyst system of the present invention can be by in first step (A), the metallic compound of a kind of inorganic carrier material and general formula I is reacted and obtains.
The solid that used solid support material is preferably finely divided, its particle diameter scope is the 1-200 micron, particularly the 30-70 micron.
The suitable carriers material is a silica dioxide gel for example, and preferably molecular formula is SiO 2AAl 2O 3Solid support material, here, a is the number of 0-2, preferably 0-0.5; These materials also are aluminosilicate or silicon-dioxide.Such product is industrial can the acquisition, for example, and from the silica dioxide gel 332 of Grace company.These solid support materials can be through Overheating Treatment, removes planar water or can be through calcining; Preferably, be preferably 100-150 ℃ and handle at 80-200 ℃.
Other inorganic materials is as Al 2O 3Or MgCl 2The mixture that perhaps comprises these compounds can be used as solid support material equally.
In the metallic compound of general formula I, preferably, M wherein 1Be the III main group element in the periodic table of elements, particularly aluminium, R 1Be C 1-C 10Alkyl, R 2-R 4Be C 1-C 10Alkyl.At M 1Under the particularly preferred situation for aluminium, u is 0, especially, and basic R 1-R 3Be identical, preferably methyl, ethyl, isobutyl-or hexyl are preferably isobutyl-.
The metallic compound of general formula I preferably joins in the suspensoid of carrier with the form of solution.Suitable solvent or suspension medium be hydrocarbon such as heptane particularly.The amount of metallic compound I can change in the scope of broad, and minimum depends on the quantity of hydroxyl in the carrier.Temperature, reaction times and pressure are unimportant; Preferably temperature is 0-80 ℃, and the reaction times is 0.1-48 hour.
Have been found that after the carrier pre-treatment, by washing, for example with hydrocarbon as pentane or hexane remove excessive metallic compound I also dry as described in carrier be useful.
Zhi Bei material can store the most nearly 6 months in this way, and is not inflammable.
In another step (B), make this material and metallocene complex and can form the reaction of metallocene ionic compound then.
Suitable metallocene complex for example is the compound of following general formula I II:
Figure A9980782600071
Here, substituting group has following meanings:
M is titanium, zirconium, hafnium, vanadium, niobium or tantalum,
X is fluorine, chlorine, bromine, iodine, hydrogen or C 1-C 10Alkyl, chlorine preferably,
R 2-R 4Be hydrogen, C 1-C 10Alkyl, the cycloalkyl of 5-7 unit, it can have C again 1-C 10Alkyl as substituting group, C 6-C 15Aryl or arylalkyl, here, two adjacent bases also can form annular group or the Si (R with 4-15 carbon atom together 13) 3, wherein:
R 13Be C 1-C 10Alkyl, C 3-C 10Cycloalkyl or C 6-C 15Aryl, Z be X or Here,
R 14-R 18Be hydrogen, C 1-C 10Alkyl, the cycloalkyl of 5-7 unit, it can have C again 1-C 10Alkyl as substituting group, C 6-C 15Aryl or arylalkyl, here, two adjacent free radicals also can form annular group or the Si (R with 4-15 carbon atom together 19) 3, wherein:
R 19Be C 1-C 10Alkyl, C 6-C 15Aryl or C 3-C 10Cycloalkyl, perhaps basic R 11Form-R with Z 20-A-group, here: R 20Be
Figure A9980782600081
=BR 22,=AlR 22,-Ge-,-Sn-,-O-,-S-,=SO ,=SO 2,=NR 22,=Co ,=PR 22Or=P (O) R 22Ist, wherein, R 21, R 22And R 23Be identical or different, each all is hydrogen, halogen atom, C 1-C 10Alkyl, C 1-C 10Fluoro-alkyl, C 6-C 10Fluorinated aryl, C 6-C 10Aryl, C 1-C 10Alkoxyl group, C 2-C 10Alkenyl, C 7-C 40Arylalkyl, C 8-C 40Aromatic yl alkenyl or C 7-C 40Alkylaryl, perhaps in each case, two adjacent bases with the atom that connects them form ring and
M 3Be silicon, germanium or tin,
A is-O-,-S-, Or
Figure A9980782600083
Here:
R 24Be C 1-C 10Alkyl, C 6-C 15Aryl or C 3-C 10Cycloalkyl, alkylaryl or Si (R 25) 3,
R 25Be hydrogen, C 1-C 10Alkyl, C 6-C 15Aryl, it can have C again 1-C 4Alkyl as substituting group, or C 3-C 10Cycloalkyl, perhaps free radical R 11With R 17Formation-R together 20-group.
In the metallocene complex of general formula III, preferably: Base X can be identical or different, but preferably identical.In the compound of general formula III a, particularly preferably be following compounds, wherein:
M is titanium, zirconium or hafnium, particularly zirconium,
X is a chlorine, and
R 8-R 12Be hydrogen or C 1-C 4Alkyl.
In the compound of general formula III b, following compounds preferably, wherein:
M is titanium, zirconium or hafnium, particularly zirconium,
X is a chlorine, and
R 8-R 12Be hydrogen, C 1-C 4Alkyl or Si (R 13) 3,
R 14-R 18Be hydrogen, C 1-C 4Alkyl or Si (R 19) 3
Useful especially compound is that wherein cyclopentadienyl is the compound of identical those general formula III b.
Useful especially examples for compounds is:
Two (cyclopentadienyl) zirconium dichloride,
Two (pentamethyl-cyclopentadienyl) zirconium dichloride,
Two (methyl cyclopentadienyl) zirconium dichloride,
Two (ethyl cyclopentadienyl) zirconium dichloride,
Two (n-butyl cyclopentadienyl) zirconium dichloride,
Two (trimethyl silyl cyclopentadienyl) zirconium dichloride.
The compound of useful especially general formula III c is a following compounds, wherein:
R 8And R 14Be identical, and be hydrogen or C 1-C 10Alkyl,
R 12And R 18Be identical, and be hydrogen or methyl, ethyl, sec.-propyl or normal-butyl,
R 9, R 10, R 15And R 16Have following meanings:
R 10And R 16Be C 1-C 4Alkyl,
R 9And R 15Be hydrogen,
Perhaps two adjacent basic R 9And R 10Or R 15And R 16Become together and have 4-12
The annular group of individual carbon atom, R 20Be
Figure A9980782600101
Or
Figure A9980782600102
M is titanium, zirconium or hafnium, and
X is a chlorine.
The example of useful especially complex compound is:
Dimethylsilane two base two (cyclopentadienyl) zirconium dichlorides,
Dimethylsilane two base two (indenyl) zirconium dichlorides,
Dimethylsilane two base two (tetrahydro indenyl) zirconium dichlorides,
Ethylene (cyclopentadienyl) zirconium dichloride,
Ethylene (indenyl) zirconium dichloride,
Ethylene (tetrahydro indenyl) zirconium dichloride,
Tetramethyl-ethylidene-9-fluorenyl cyclopentadiene base zirconium dichloride,
Dimethylsilane two bases two (3-normal-butyl-5-methyl cyclopentadienyl) zirconium dichloride,
Dimethylsilane two bases two (3-normal-butyl-5-ethyl cyclopentadienyl) zirconium dichloride,
Dimethylsilane two bases two (2-methyl indenyl) zirconium dichloride,
Dimethylsilane two bases two (2-isobutyl-indenyl) zirconium dichloride,
Dimethylsilane two bases two (2-positive definite base indenyl) zirconium dichloride,
Diethylsilane two bases two (2-methyl indenyl) zirconium dichloride,
Dimethylsilane two bases two (3-methyl-5-methyl cyclopentadienyl) zirconium dichloride,
Dimethylsilane two bases two (3-ethyl-5-sec.-propyl cyclopentadienyl) zirconium dichloride,
Dimethylsilane two bases two (2-methyl indenyl) zirconium dichloride,
Dimethylsilane two bases two (2-methylbenzene indenyl) zirconium dichloride,
With dimethylsilane two bases two (2-methyl indenyl) hafnium dichloride.
The compound of useful especially general formula III d is a following compounds, wherein:
M is titanium or zirconium,
X is a chlorine,
R 20Be
Figure A9980782600111
Or
A is-O-,-S-,
Figure A9980782600121
And
R 8-R 10And R 12Be hydrogen, C 1-C 10Alkyl, C 3-C 10Cycloalkyl, C 6-C 15Aryl or Si (R 19) 3, perhaps two adjacent bases become the annular group with 4-12 carbon atom together.
Can preferably make the cyclic hydrocarbon negatively charged ion of corresponding replacement and the halide reaction of titanium, zirconium, hafnium, vanadium, niobium or tantalum by the synthetic such complex compound of known method.
At organometallic chemistry journal (Journal of OrganometallicChemistry), 369 (1989), the example of corresponding preparation method has been described among the 359-370.
Also might use the mixture of various metallocene complexes.
Suitable can form metallocene ionic compound, particularly uncharged strong lewis acid, contains the cationic ionic compound of Lewis acid and contains Bronsted acid as cationic ionic compound.
As uncharged strong lewis acid, the compound of general formula I V preferably:
M 4X 1X 2X 3IV is here:
M 4Be the element of periodic table of elements III main group, particularly B, Al or Ga, B preferably,
X 1, X 2And X 3Be hydrogen, C 1-C 10Alkyl, C 6-C 15Aryl, each is at the alkylaryl, arylalkyl, haloalkyl or the halogenated aryl that 1-10 carbon atom are arranged on the alkyl and 6-20 carbon atom arranged on aryl, perhaps fluorine, chlorine, bromine or iodine, particularly halogenated aryl, preferably pentafluorophenyl group.
Particularly preferably be wherein X 1, X 2And X 3Be the compound of identical general formula I V, preferably three (pentafluorophenyl group) borine.
The suitable cationic ionic compound of Lewis acid that contains is the compound of general formula V:
[(Y A+) Q 1Q 2... .Q z] D+V is wherein:
Y is the element of periodic table of elements I-VI main group or I-VIII subgroup,
Q 1-Q zBe single electronegative group, as C 1-C 28Alkyl, C 6-C 15Aryl, each 6-20 carbon atom arranged on the aryl and on alkyl, have 1-28 carbon atom alkylaryl, arylalkyl, haloalkyl or halogenated aryl, can also have C 1-C 10Alkyl as substituent C 1-C 10Cycloalkyl, halogen, C 1-C 28Alkoxyl group, C 6-C 15Aryloxy, silyl or sulfydryl (mercaptyl),
A is the integer of 1-6,
Z be 0-5 integer and
D is the poor of a-z, and condition is that d is more than or equal to 1.
Specially suitable is carbocation, oxygen positively charged ion and sulphur positively charged ion and cationic transition metal complex.Can should be mentioned that trityl group positively charged ion, silver-colored positively charged ion and 1 especially, 1 '-dimethyl-ferrocenyl positively charged ion.They preferably have the compound of non-coordinate gegenion, particularly boron, described in WO 91/09882, and four (pentafluorophenyl group) borate preferably.
In WO 91/09882, described and contained Bronsted acid as positively charged ion be preferably the ionic compound of non-coordination gegenion equally; Preferred cation is N, N '-xylidine positively charged ion.
The particularly preferred aromatics boron compound that is to use is as forming metallocene ionic compound; Especially, use xylidine four (pentafluorophenyl group) borate.
The consumption that can form metallocene ionic compound is the 0.1-10 equivalent preferably, is benchmark with metallocene complex III.
Metallocene complex is unimportant with the reaction conditions that can form metallocene ionic compound, but preferably reacts in solution.Suitable solvent is hydrocarbon particularly, and aromatic hydrocarbon preferably is as toluene.
In said mixture, add as A then) described in the material for preparing.With the inorganic carrier material is benchmark, and the amount of metallocene complex is that 0.1-10 weight % is specially suitable.The condition of this reaction is not important equally; Have been found that temperature in 20-80 ℃ of scope, the reaction times was useful especially in the scope at 0.1-20 hour.
Separate then as B) described in the material of acquisition, and can keep at least 6 months.
At another step C) in, by B) in the metallic compound reaction of the material that obtained and general formula I I.If use metallocene complex with its dihalide form, this step is used to activate described metallocene complex substantially.Yet even use with activity form under the situation of metallocene catalyst, in order to obtain optimum activity, the contact of metallizing thing II also is necessary.Can put at any time and activate, promptly add by B in dosage in reactor) in before the material that obtained, among or afterwards.Preferably by B) in the material that obtained added under the condition of reactor by dosage and activated.
In the metallic compound of general formula I I:
M 2(R 5) o(R 6) p(R 7) qII is wherein:
M 2Be the metal of the III main group of basic metal, alkaline-earth metal or the periodic table of elements, i.e. boron, aluminium, gallium, indium or thallium,
R 5Be hydrogen, C 1-C 10Alkyl, C 6-C 15Aryl, each is at the alkylaryl or the arylalkyl that 1-10 carbon atom are arranged on the alkyl and 6-20 carbon atom arranged on aryl,
R 6And R 7Be hydrogen, halogen, C 1-C 10Alkyl, C 6-C 15Aryl, each is at the alkylaryl, arylalkyl or the alkoxyl group that 1-10 carbon atom are arranged on the alkyl and 6-20 carbon atom arranged on aryl,
O is the integer of 1-3,
With
P and q are the integers of 0-2, and here, the summation of o+p+q is equivalent to M 2Valency.
Following compounds preferably, wherein:
M 2Be lithium, magnesium or aluminium and
R 5-R 7Be C 1-C 10Alkyl.
The metallic compound of particularly preferred general formula I I is n-Butyl Lithium, normal-butyl-n-octyl magnesium, normal-butyl-n-heptylmagnesium, triisobutyl aluminium, triethyl aluminum and tri-n-hexyl aluminum.
Step C) reaction conditions in itself is unimportant.Temperature, reaction times and pressure depend on that reaction promptly activates the time point that carries out.
Be characterised in that in the inventive method, described supported catalyst or its precursor are contacted with a small amount of Lewis base.Being added in the Preparation of catalysts process of this Lewis base adds as early as possible.In an advantageous embodiment of present method, make A set by step) in handled catalyst precursor contact with Lewis base, promptly before this catalyst precursor loads with metallocene complex, make Lewis base and contact with the metallic compound of general formula I preprocessed catalyst carrier.In this way, Lewis base is coated on the carrier effectively, thereby Lewis base is begun when this metallocene complex is coated on the carrier immediately to the provide protection of metallocene complex.
It is particularly advantageous wherein using the method for the metallocene complex that uses with its metal dihalides form.In this case, at the metallocene dihalide at step C) in the activation before, it is particularly advantageous that Lewis base contacts with described supported catalyst or its precursor.
The mode that wherein adds Lewis base in described supported catalyst or its precursor is not important usually.In general, Lewis base is dissolved in the organic solvent (as toluene), and this solution is contacted with solid support material.
In supported catalyst or its precursor, add Lewis base ahead of time and produce the enrichment of Lewis base on carrier surface, therefore make it might reduce the Lewis base consumption in a large number.It is the Lewis base of every mole of metallocene complex 0.3-＜2 mole that an advantageous embodiment of the present invention provides consumption.The ratio that particularly preferably is Lewis base and metallocene complex is the 0.5-1.5 mole: 1 mole.
Suitable Lewis base is the compound that have all kinds of materials of following character: they should be able to coordination a little less than the metal center of metallocene complex, its mode should make that they can be treated, and polymeric alkene replaces from this ligand.The favourable compound that is applicable to the inventive method is, for example, and aromatic amine, alkylaryl phenol and steric hindrance type ether and amine.In aromatic amine, particularly preferably be tertiary amine, for example, C 1-C 4Dialkyl aniline, particularly xylidine.The aromatic nucleus of these ammonia can be replaced by various electronics or the electron-withdrawing substituents given, thereby changes the coordination intensity of nucleophilicity and compound.This is equally applicable to alkylaryl phenol.Alkylaryl phenol contains the alkyl with 1-10 carbon atom usually, can be substituted on aromatic nucleus equally.Have been found that favourable substituting group particularly electron-withdrawing group such as fluorine atom.The example of particularly advantageous Lewis base is the penta fluoro benzene methyl ether.As steric hindrance type ether and amine, can should be mentioned that 2,6-two-tertiary butyl aniline, 2,2,5,5-tetramethyl-tetrahydrofuran (THF) or 2,5-di-t-butyl furans.
The supported catalyst system that obtains by described novel method has higher productivity than similar known catalysts system, does not introduce a large amount of extractable matter simultaneously in polymkeric substance.Catalyst system on the described novel carriers is specially adapted to polymerization in homogeneous phase or ethene or the propylene and the C of ethene or propylene 3-C 10The copolymerization of-alpha-olefin.As C 3-C 10-alpha-olefin can be used on all common alpha-olefins that are used as comonomer in ethene or the copolymerization of propylene.Can should be mentioned that butylene, hexene and octene especially.Yet the 1-alkene of cycloolefin and Geng Gao and alkene generally can be as the monomers of polymerization in homogeneous phase or copolymerization.
Supported catalyst system of the present invention can be used for various polymerization processes, in the process that particularly suspends and the gas phase process.It is particularly advantageous using supported catalyst of the present invention in the gas-phase polymerization processes of alkene.These gas-phase polymerization processes are known for being familiar with the person skilled in art.For example, can in the gas phase that stirs, carry out polymerization, carry out but particularly preferably be in gas-phase fluidized-bed.
Embodiment
Embodiment 1-4:
(ES 70 X, Crosfield produces) 130 ℃ of heating 6 hours, are suspended in the toluene solution (8.5 milliliters 2M solution) of triisobutyl aluminium then 6 gram silica gel.After 2 hours, filter out solid support material, be suspended in then in 50 milliliters of toluene.With short time interval, in described suspension, add 242 milligrams of xylidine-four-pentafluorophenyl group borates, 3 milliliters 0.1 mole (0.3 mmole) N, N '-xylidine solution and 121 milligram of two (n-butyl cyclopentadienyl) zirconium dichloride (0.3 mmole) in toluene.Reaction mixture was also stirred 80 ℃ of heating in 30 minutes.Under reduced pressure discharge solvent subsequently.This produced can the free flowing powder form catalyzer.Use is similar to this preparation process, has prepared the catalyzer with following Zr, B and xylidine ratio:
????Zr ????B Xylidine
Embodiment 1 ????1 ????1 ????1
Embodiment 2 ????1 ????1 ????0.5
Embodiment 3 ????1 ????1 ????3
The comparative example ????1 ????1 ????0
The polymerization of ethene
10 liters steel autoclave of a stirring is carefully used purging with nitrogen gas, and be heated to 70 ℃ polymerization temperature, pack into then 4.5 liters of Trimethylmethanes and 150 milligrams of butyl octyl magnesium (2 molar solutions in heptane).Use 0.5 liter of other Trimethylmethane washing catalyst carrier then, and with ethene to described autoclave be pressurized to total pressure be 38 the crust.By being metered into the constant pressure in the other ethene maintenance autoclave.After 90 minutes, end polymerization by the decompression of described autoclave.Form with free flowing powder obtains polymkeric substance.
Catalyst mode productivity (gram polymkeric substance/gram catalyzer)
Embodiment 1 5100
Embodiment 2 2800
Embodiment 3 600
The comparative example 2400
Described embodiment shows, even very small amount of Lewis base also can cause the best of productivity to increase.

Claims (10)

1. a method for preparing supported catalyst comprises the following steps:
A) metallic compound of a kind of inorganic carrier material and general formula I is reacted:
M 1(R 1) r(R 2) s(R 3) t(R 4) uI here
M 1Be the III of basic metal, alkaline-earth metal or the periodic table of elements or the metal of IV main group,
R 1Be hydrogen, C 1-C 10Alkyl, C 6-C 15Aryl, each is at the alkylaryl or the arylalkyl that 1-10 carbon atom are arranged on the alkyl and 6-20 carbon atom arranged on aryl,
R 2-R 4Be hydrogen, halogen, C 1-C 10Alkyl, C 6-C 15Aryl, each is at the alkylaryl, arylalkyl, alkoxyl group or the dialkyl amido that 1-10 carbon atom are arranged on the alkyl and 6-20 carbon atom arranged on aryl,
R is the integer of 1-4
With
S, t and u are the integers of 0-3, and wherein, the summation of r+s+t+u is equivalent to M 1Valency,
B) make as A) described in the material that obtains with metallocene complex with can form metallocene ionic compound and react, and
C) material of gained and the metallic compound of general formula I I are reacted:
M 2(R 5) o(R 6) p(R 7) qII is wherein:
M 2Be the metal of the III main group of basic metal, alkaline-earth metal or the periodic table of elements,
R 5Be hydrogen, C 1-C 10Alkyl, C 6-C 15Aryl, each is at the alkylaryl or the arylalkyl that 1-10 carbon atom are arranged on the alkyl and 6-20 carbon atom arranged on aryl,
R 6And R 7Be hydrogen, halogen, C 1-C 10Alkyl, C 6-C 15Aryl, each is at the alkylaryl, arylalkyl or the alkoxyl group that 1-10 carbon atom are arranged on the alkyl and 6-20 carbon atom arranged on aryl,
O is the integer of 1-3,
With
P and q are the integers of 0-2, and here, the summation of o+p+q is equivalent to M 2Valency, it is characterized in that the supported catalyst of Huo Deing or its precursor contact with Lewis base with every mole of metallocene complex 0.1-＜10 mole dosage in this way.
2. according to the method for claim 1, it is characterized in that, make as steps A) in handled catalyst precursor with as described in Lewis base contact.
3. according to the method for claim 1, it is characterized in that, use the metallocene complex of its metal dihalides form, and make described Lewis base at step C) reaction before contact with described supported catalyst or its precursor.
4. according to the method for claim 1-3, it is characterized in that the consumption of described Lewis base is every mole of metallocene complex 0.3-＜2 mole.
5. according to the method for claim 1-4, it is characterized in that, use a kind of Lewis base that is selected from aromatic amine, alkylaryl phenol and steric hindrance type ether and amine.
6. according to the method for claim 1-5, it is characterized in that employed Lewis base is an xylidine.
7. according to the method for claim 1-6, it is characterized in that the described metallocene ionic compound that can form is the aromatic series boron compound.
8. supported catalyst system that obtains according to the method for claim 1-7.
9. supported catalyst system according to Claim 8 is in the polymerization in homogeneous phase of ethene or propylene or at ethene or propylene and C 3-C 10Application in the copolymerization of-alpha-olefin.
10. the application of supported catalyst system in the vapour phase polymerization of alkene according to Claim 8.
CN99807826A 1998-06-25 1999-06-12 Method for producing supported catalyst system Pending CN1307596A (en)

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